Ampholytic metal esters and the method of their preparation



March 21, 1961 B. RUDNER ETAL AMPHOLYTIC METAL ESTERS AND THE METHOD OF' THEIR PREPARATION Filed Nov. 17. 1959 SCNE .522? mmuz 538m mmtz ,EEEEE .l sz

AMPHOLYTIC lVIETAL ESTERS AND THE METHOD F THEIR PREPARATION Bernard Rudner and Mead S. Moores, Pittsburgh, Pa., assignors to Kappers Company, Inc., a corporation of Delaware Filed Nov. 17, 1959, Ser. No. 853,555

Claims. (Cl. 260-448) This invention relates to novel polymeric and nonpolymeric organic electrolytes. In one specific aspect, it relates to novel intramolecularly and intermolecularly condensed metal ester betaines. In a further aspect, it relates to a novel method by which the betaines of the invention are made.

In recent years, metal and metalloid esters have become increasingly important in industry as lubricants, additives and heat-resistant materials. The known esters of this type have the common disadvantage of being readily susceptible to hydrolysis. Thus, the simple organic borates, useful as fuel additives, would be far more valuable if they were less readily hydrolyzable. The socalled inorganic polymers of boron and aluminum, e.g.

would be in great demand vas heat-resistant materials for rockets if they were not subject to almost instantaneous hydrolysis.

Quite surprisingly, we have discovered novel ionizable esters containing either boron or aluminum which, even after 24 hours in aqueous solution, are recoverable as such. This resistance to hydrolytic cleavage is surprising, since the ionizable esters known heretofore, e.g. sodium tetramethoxyborate, are immediately converted by water to inorganic salts and organic alcohols.

The novel metathetical transestenfication reaction of the invention provides a method for preparing betaine esters, both unimeric and polymeric, of boron or aluminum. The products of the invention, which are remarkably elective as antistatic agents, are the first known betaine esters in which boron or aluminum is the negatively charged element. The novel polymeric materials possess a further unique characteristic: they are the rst known polymeric betaines in which both types of charged atoms are found in the spine of the polymer.

It is, therefore, an object of the present invention to provide a new generic class of both polymeric and nonpolymeric chemical compounds having a common betaine structure and which `are useful, inter alia, as antistatic agents. It is a further object to provide a novel metathetical transesteriiication method of making the new betaines.

In accordance with the invention, we have discovered new and useful betaines corresponding to the generic formula:

In the above formula land the formulas that appear hereafter (unless special designations are given), Q is a quaternized nitrogen or phosphorus `atom and M is a tetracovalent negatively charged boron or aluminum atom, n is an integer having a value of l-6 and m is an integer having a value of 1-25. The R substituent is an aliphatic 2,976,307 Patented Mar. 2l, 1961 which they are respective substituents, they form a heterocycle of the group consisting of:

depending on whether one, two or three sets of R+R react with each other. Y+ represents the cation of the starting metalate and X- represents the anion of the onium salt used in the preparative reaction.

The nature of the products of the invention can be more clearly understood by referring to the accompanying drawing.

'Ihe drawing -shows the structures of possible products arising from the reaction of tetrakis-(Z-hydroxyethyl) am monium chloride with sodium tetramethoxyborate. As is seen in the drawing, the initial reaction between the onium salt 1 (or similar salts listed in Table A, infra) and the metalate salt 2 (or similar slats listed in Table B, infra) is a metathesis which yields the simple salt Y+X and the so-called onium-ate uncondensed salt 3. The salt 3 is isolable only under special conditions. During ordinary conditions of reaction work-up, most of the uncondensed salt 3 reacts intramolecularly to give as a first product either the simple mono-condensate 4 or its Y+, X'- adduct 5. If Q and M each have only one degree of condensation functionality, as would be the case using a salt the only products obtainable at reasonable temperatures would be the analogs of 4 and 5. Since, however, the starting metalate salt is always tetrafunctional, further stepwise condensation can occur under reaction conditions of increased severity, as will be explained hereafter.

In the case where Q has at least two transesteriable groups (in the example of the drawing it has four transesteriable groups), both intramolecular condensation and intermolecular condensation can occur on the elimination of the next mole of alcohol to give both the unimeric product 10 and the essentially linear polymeric product 6. lf the hydroxyl group of hydroxyalkyl radical is more than two carbon `atoms away from Q, the linear product 6 will greatly predominate because of steric re strictions on l2 membered ring formation. However, when the hydroxyl groups are only 1 or 2 atoms removed from the Q atom, formation of 6-8 membered rings seems to be preferred over linear configurations.

On further loss of alcohol by condensation, the linear polymer 6 can be converted to a branched polymer 7 wherein the branch chains extend from the nitrogen atom (designated in the drawing as Branched Polymer, Type I), a branched polymer 8 wherein the branch chains extend from the boron atom (designated in the drawing as Branched Polymer, Type Il) or a macrocycle 9.

The unimeric product 10 can (in the example shown in Y ducts, e.g. 5, yare the most stable type and are altered only balanced ion adducts are likely to be formed. If, in addition, the onium and metalate salts have a different degree of functionality, as in the case of the salt meric product 11 is capable of intermolecular condensa- H3C 002115 tion to form linear polymer 12 (structure not shown in 5 s All.. the drawlng). 1Structures10, 11-and 13 are represented [mmmcgmoozmoms] in the general formula by indicating that individual R H3C OCEHB and R' substituents are taken collectively with the Q and transesterifcation will lead to products containing appreci- M on which they are representative substituents to form a able quantities of the unbalanced adducts, e.g.

heterocycle corresponding to these structures. The particular structure formed depends` upon the degree of transesterication; i.e. the number of sets of R-l-R that react with each other. 20

We have noted that our novel condensation products are capable of adduct formation was of the type illustrated by compound 5 in the drawing. It is also possible, upon further condensation of the product to form adducts or ionic sans with the ons X or Y+ These sans are 25 results in the formation of polymers containing double illustrated by 14 and 15 in the drawing and are set forth rmg Segmers Such as hnar polymer 21 branched poly' in the formula given hereabove by equating lthe R sub- H161 Z2, macrocycle 2? and netted polymer 24 (structure sement to (CnnlmMR'ai-w or the R' 'substituent of Shown 1n the ifawmgto (CnHmmmQRspXvwherein the cation Y+ Q1- the The degree-ofmtermolecular condensation and thedeanion X associates itself with the molecule to compen. 30 gree of intramolecular condensation, which determines sate for VVthe ext-ra negative or positive charge present on` the Structure 0f the Product CNB-ined, depends 10 a large the spine of the molecule. When the initial metathesisextent upon the reaction conditionsA selected, as will be isrun under conditionsy favoring complete separationof explained in detail hereafter. Thus, under certain conthe salt Y+X from theproduct 3 (or its analogs), there is relatively little tendency to fornr ionl adducts of the typesl illustrated by 5, 14 or 15. Moreover, under such conditions, any type of unbalanced charge adduct e.g.

The unimeric product 10 is capable of intermolecular mers, such as linear polymer 16, branched polymer 17, branched polymer 18 and macrocycle 19. The structure of polymers 17, 18 and 19 is not shown in the drawing. The formation of a netted polymer 20 can also occur.

21. LinearA polymer 6 can be converted tor linear polymer of our products occur as mixtures and because of their compatability they are useful as such. Y

The compounds ofthe invention are prepared by retends as much asy possible, to nd a complementary organic molecule with which to react, las is shown in lthe` following equation:

p Home. ri-[omuo'ocnnaz Na+ (CHionB-(O-CHuIiIC-Hm 01m-N801 C (IlHs CH3 10i-[cingoli (o onen When an appreciable amount of initially formed salt Y+X cannot be separated from the uncondensed organic product of metathesis, asin Example III, wherein sodium iodide, being soluble, remains, all three types` of organic ion adducts are formed.` Y The balanced ion ad-Y acting in an inert organic liquidV an onium salt of the by sublimation or chemical reaction. with a metalate salt of the formula:

To some extent, the formation of both balanced and l l R' Y unbalanced lon adducts 1s dependent on the nature ofthe l starting onium ,and metalate salts. If X- and Y+ are so Y Y* R 'MTR chosen kthat they represent the anion of an acidy weaker B than H+MR4- or the cation of a base weaker than .'Inthe'formula's Q, M, m andn have the values given [R3Q(CH2Q)mH]OH-, then both. balanced` and? un- 75 in describing the 'compoundsof the invention. Rais' an condensation to form polymers having single ring seg-Y Intermolecular condensation Iof unimeric product 10 alsoV ditions many of our novel productsfare readily intercon vertible. For example, cationic adduct 14 can react with anionic adduct 15 to produce a linear polymer such asf 16 or to linear polymer 12 by further condensation. ByY` 40 removing alcohol from balanced adducty 5- it is possibler C 3 to make cationic adduct 14 and anionic adduct 15; MostA aliphatic radical having from 1-20 carbon atoms inclusive, benzyl, aminoalkyl, alkanoylaminoalkyl and sense, insufficiently basic to be quaterni'zed by a halohydrin. The corresponding phosphine, triphenylphosphine, can be readily quaternized, but the product does not undergo our novel metathetical transesterilcation reaction. Many of the metalate salts can be conveniently prepared by reactions such as those described by H. C. Brown and E. J. Meade, I. Am. Chem. Soc., 78, 3614 (1956).

Typical useful onium salts'are listed hereunder in Table A by name and structure and useful metalate salts are given in Table B. The salts of Table A react with those of Table B in the manner shown in the drawing and described in detail in the examples that follow.

TABLE A Suitable onum compounds Name Structure CHa . Trlmethyl2hydroxyethylammonium chloride.

2. Diallyl-bis-(2-hydroxypropyl) ammonium bisulfate.

3. Benzybtris- (5-hydroxyamy1) ammonium fluoride.

phonium ehlorlde.

. Tris-(benzyldlmethylhydroxymethylphosphonium)phosphate.

Tetrakis-(Z-hydroxyethyDammonium perchlorate. y

hydroxypropynammonium trichloro- Ha a CHgCHzOH l 12. 3- (o ctadeeenylamino)propyltris (2- [CHaCeEhSOnl' hydroxyethy Dammomum tosylate.

CHiCHzOH C HzC H2 `H` 13. N,NBis(2hydroxypropyl)pipera HO CHCHZN NCHgCHOH SO:

zinium sulfate.l

C Ha C Hz C H2 C H: H500 CHzCHqOCHrCHzOCI-LCHQOH 14. Phenylbenzylbis (-hydroxyethyl- Brethoxyethoxy)phosphonium bromide.

HsCaCHn CHZCHQOCHZCHiOCHaCHzOH CHzC H;

15. Di-(2-EthylhexyU-bis (5A-hydroxy; CHaCHzCHzCHzCHCHz }C2H4O)5CH1CH1OH O pentaethoxyethyhammomum methosulfate. N CHsO l O CHSCHgCHzCHz CHsCHzCHzCHz TABLE' B Suitable metalate compounds Name Structure t H CH;Y 1. Lithium Neopeutoxytrihydroborate Li+ HIIBOCHglClEh i on,

OCzHs 2. Lithium ,Amyltrlethoxyaluminatee...r.-. Li CHsCH2CHgCHgCHzAl-0Cgl5f i vCH3 H CH3 SiMagnesium Triisopropoxyhydroborate; VMg++V (IJHB l CHxCHOBH H3C-HCH 2 H 4. Aluminum Borohydride Al+++ Hl'BH Elf a CH3 v 5. Potassium Tetramethoxyaluminate K+ CHaOAIOCIEI;

` Y y CH3u f H (CHahCOlO C (CHM` 6. Sodium Tri-t-butoxyhydroaluminate Na+ (INCE):

t CnHa 7. Calcium Triphenylmethoxyborate Ca++ CoHBOCHs CHaO 00H; 8. Potassium Dimethoxyethylenedioxyborate- K+ \B/ CHzO/ \O CH3 9. Sodium Triphenoxyhydroaluminate Na+[(C5)3AlH] Since the betaines of the invention areyforrned as a result of the novel transesterication between the onium cation and the metalate anion, the nature of the anion X*- which is associated with theonium salt and the cation Y+ which is associated with the metalate salt is unimportant. The preferred choice of reactants and, thus, the respective values of X* and Y+, are governed to some extent by the commercial availability'of the starting onium and metalate salts. Ease of handling and ease of product Work-up also influence the choice.

The onium halide salts are the most readily available, although, as seen in Table A and in the examples, the method of the invention Works equally Well when the anion X- is other than halide. Speciiic, but non-limiting, organic and inorganic examples of the anion X'* are as follows: acetate, phosphate, diethylphosphate, benzylphosphonate, diphenylphosphinate, monocetyl sulfate, methylsulfonate, hexafiuorophosphate, bisulfate, thiosul fate, tetrafluorosilicate, tetralluoroborate, sulfate, nitrate, and the'like;

Where products free of ion adducts are desired, we have found it desirable to choose X- and`Y+ soV that they are capable offorming, during the metathetical 'reaction, simple organic solvent-insoluble electrolytes Y+X*. In this case, the resulting salt Y+X* is theoretically derived from the strong acid H+X and the strong base Y+OH', both of which are approximately equal in ionic strength and preferably stronger than the corresponding trifluoroacetate, and the like.

Other useful examples of the cation Y+ are zinc, lead, germanium, zirconium, mercury, gallium, cadmium, and the like.

In preparing the compounds of the invention, it is generally suitable to contact theonium salt with a metalate salt in an inert organic liquid, allow the reaction to proceed to completion, and then recover the resultant product, products or product mixtures by standard laboratory techniques: v

The liquid organic medium used for the reaction must be an anhydrous inert organic liquid such as hydrocarbons, e.g. tetralin, benzene, cyclohexane, xylene, decane, and the like; halohydrocarbons, c g. chloroform, bromobenzene, and the like; ethers, e.g. dimethyl ether, tetrahydrofuran, dioxane, diethyleneglycoldimethyl ether, and the-like; and polar nitrogeneous liquids, e.g. pyridine,

acetonitrile and-dmethylformamide.- Anhydrous conditions must be maintained during metathesis and transesteriiication.

The preferred liquid medium for the invention is the alcohol ROH wherein R' is the alkyl portion of the lower alkoxy group which goes to form the alcohol eliminated during the transesterication. For example, if the metalate anion is a tetramethoxyborate, methyl alcohol will be eliminated during transesterification and the preferred liquid medium is methyl alcohol. The use of alcohols other than that eliminated during the particular metathetical transesterication reaction being conducted is not recommended, since such alcohols are not inert to the reactants and products, an equilibrium mixture results from transesterication with the solvent.

The order of addition of the reactants is not critical.

,.However, as a matter ofY convenience, itwis sometimes preferred to add a solution of the onium salt in the inert organic liquid to a similar solution of the metalate salt.

The reaction temperature can range conveniently from the temperature of liquid nitrogen (-195 C.) to the reflux temperature of the particular solvent used. Thus, as a practical matter, the temperature used can be varied between 195 C. and about 250 C. The temperature chosen for any given reaction is determined to a large extent by the nature of the desired product. Thus, if it is desired to obtain a pure uncondensed onium-ate salt where no other R is an alkanol residue and only one R is alkoxy, slurries of each of the reactants in, e.g. dioxane, can be mixed at room temperature and the reaction will proceed as follows:

If a simple condensation is desired, the reaction mixture can be carefully maintained at a temperature of e.g. -50 C. to cause transesteriiication and elimination of one mole of alcohol.

Prolonged heating causes the formation of a fully condensed salt, e.g.

The procedure described hereabove will not give a pure product readily; nor is it generally necessary, for purposes of the invention, to obtain a pure product. Since uncondensed salts are more stable when at least one R is hydrogen and when the alkylene radical R is branched at the oxygen-bearing carbon, it follows that the preparation of salts such as [P(CH2CH2OH)4]+[B(OCH3)4] and its simple transesterication product,

require less mixing and lower temperatures than do the corresponding products mentioned above. Obviously, the extent of temperature elevation and the extent of duration of heating are related. We prefer to maintain our reactants at the lowest temperature at which reaction proceeds satisfactorily until weight loss indicates that the desired number of moles of alcohol have been eliminated. Generally speaking, to obtain the maximum degree of condensation it is best to heat the reaction mixture (after filtration to remove the inorganic salt) to a constant weigh ata temperature of about 12S-250 C.

The reaction works well at atmospheric pressure, al though sub-atmospheric or super-atmospheric pressures can be used. Itis often convenient to work under vacuum, since this promotes removal of the alcohol which is, in most cases, the second product of our novel transesteriiication. Alternately, the alcohol formed may be removed, if desired, by passing a stream of an inert gas, e.g. dry nitrogen, through the reaction mixture. (If all of the R' substituents are hydrogen, hydrogen rather than an alcohol will be split oi during transesterilication.) The extent of pressure reduction depends on the nature of both the starting materials and the desired product. Thus, when the product wanted is a lower condensate of an onium-ate salt in which the two starting compounds have the same degree of functionality (i.e.

products of types 10 and 11 of the drawing), the use of a slight vacuum, e.g. 200 mm. of Hg, is advantageous. If, however, it is desired to convert the simple condensate 3 into a high polymer, the use of a relatively high vacuum, e.g. l-l5 mm. of Hg, is desirable. An equally high vacuum is useful when working with the less stable unbalanced cationic and' anionic adducts.

The mole ratio of the reactants is not critical, but it does influence to some extent the nature of the products that can be obtained. To obtain products having a maximum degree of purity, it is desirable to use substantially stoichiomertic quantities, based upon the degree of conversion desired. Thus, to convert [(CH3)3PCH2CH2OH]+ to equimolar quantities are preferable.

the stoichiomertic ratio is 4 moles of onium compound to one mole of metalate.

The reaction time required to produce the novel cornpounds from the appropriate intermediates is dependent upon conditions of temperature, pressure, -mole ratio, thoroughness of contact, and intrinsic process variations apparent to those skilled in the art. The metathetical reaction is almost instantaneous if the salt Y+X formed is insoluble in the particular organic medium selected, but in order to obtain maximum yields it is advisable to stir the mix for 2-4 hours at the reaction temperature desired. As we have noted, the time required for condensation is best measured by loss in weight of the reaction mixture.

Our invention is further illustrated by the following examples.

EXAMPLE I Under anhydrous conditions, 103.9 g. trimethyl borate were added dropwise to a stirred solution consisting of 54 g. dry sodium methoxide in 250 ml. of absolute methanol. Immediate precipitation occurred. The reac tion mixture was ltered in the absence of moisture and dried to give 148 g. of sodium tetramethoxyborate (94% yield). The product was a very hygroscopic white solid, melting at 253-25 8 C. and soluble in water and methanol. The reaction is shown hereunder:

Triethanolamine, 149.2 g. in 200 ml. methanol, was treated at 0 C. with 156.2 g. methyl iodide. The mixture was allowed to stand overnight and then filtered free of 42.2 g. triethanolamine hydriodide (photosensitive crystals). The filtrate was evaporated in vacuo -to give 254.4 g. of a red oil which, on trituration with acetone, followed by vacuum drying, gave 237.3 g. of a thick orange oil. The product represented an 81% yield of methyl-tris-(Z- hydroxyethyl) ammonium iodide. (Analysis: I, Calcu- Vlated as the colorless sublimed bicyclic betaine).Y The deionizedwatmer, was stirredat reliux for fourvhoyurs 'witha75 chloride in 100ml. of ethanol.

Y 11 l2 lated 43.6% ;1 FoundV 43.8%.) 'I'lieY qil'aternization is 59.3 g. freshly prepared silverchlonde and thereafter shown below: cooled and filtered. The combined liltrate and washings,

- n y evaporated dry in vacuo, gave 64.4 g. (93.7%) methyl- CH3I+N(C2H4OH) 39 [CH3N(C2H4OH) 3] +I tris-(2-hydroxyethyl)'ammonium chloride which appear- Running the quaternization in the absence of solvent gave 5 ed as `colorless deliquescent crystals, melting at 181- ahigher yield of product richer in the amine hydriodide. 190 C, and containing 18.1% chlorine (theory 17.7%

EXAMPLE III' v A 29.4 Ig. quantity of the product of Example II in 50 AgI-i- [CH3N(C2H4OH)3+C1- m1. dry methanol waslmixeci1 with 15g g. of the product 10 e EXAMPLE V of Example I -in 50 m met ariol. T ye reaction mixture x .Stood overnight at 10 C. and gave a clear, colorless maf'rgrdpgcfsgf glafngilelgllgog sohmon The SolutloI-l was evaporated m Vauo at Ipm 50 ml. of methanolv to give an immediate white precipitate. temperature" The dlsuu'a was .m'thanfl .contgmng Entretien yielded 5 g. sodium ehiende (86% of theory). only? trace of (.CII3O)3B, The resldue Weighing 3 '7 g" 15 Evaporation ofthe combined methanol wash and filtrate appeared as a ngld foam Crushable o a Whlte Powder at room temperature gave asl a clear colorless gum, melting at'228-30 C. with discoloration, and readily sol- 26 5 crude 2 [methymsizhydroxyetyl) ammonuml uble in Water (with alkaline reaction). Although the etoxg' methox berate betaine product shouldhave contained one equivalent of sodium y y iodide, Xray diiraction showed absence of this as such, c las well as the absence of polymers. Fractional precipitation using various solvents failed to remove or concentrate organics or inorganics, and, therefore, the product wasbelieved to be the. loose adduct (Ho oinijaL-oiuioi one as established by stoichiometry.

[CHiNiHioEo a] oi-+NaB (0 CHe)i- (11H3 Nao1+cmon+wmo noOiHiNoeHion),

EXAMPLE VI A solution of 20.7 g. of the product of Example I in 75 ml.V methanol was added dropwise to a stirred solution of 25.0 g. tetrakis(hydroxymethyDphosphonium chloride in 75 ml. of methanol over a periodof ZOminutes at just below reflux temperature. The resulting mixture CHzCHzO oneri-fonicneo-B'o om 1'- cmcnio rie which is relatively unstable to heat. Heating the product at 20D-,230 C. in vacuo gave as a sublimate a crystalline White solid, melting at 23S-6 C. with decomposition Was qulckly Cooled and efporated dry 1F Vacuum at room and sublimatiom The crystals were ha1ide free, and temperature. The alkalinity 'of thesodium tetramethoxy- Water and methanol' soluble (alkaline reaction). The 35 borate caused some destruction of the phosphomum salt Structure of the product was assumed to be: (see reactions below), leading to the formation of some trimethyl borate and formaldehyde, but the major part CHQCHZO of the reaction Went as desired.V Evaporation left as .L residue the crude, glassy, water-soluble polymeric phos- CHN CHCH20BOCH 40 phoniurn tetraalkoxyborate i amonio 1methyl5methoxy1-aza-S-bora 4,6,11 trioxabicyclo- [3.3.3]undecane betaine. After being held at 230 240 C. in vacuo for one hour a `5.0 g. sample of the colorless adduct was converted to 3.25 g. of involatile glassy polymer soluble only in water (0.67 g.V being isomelting atY approximatelyV 190 C. with decomposition. On the basis of the analytical data, the stoichiometry of the reactions can be .Written as:

(5.5 g.) (9.9 g.) (10 g.) (12.6 g.) 130.2% n

P (CH2OH)a+CHsOH-i-CH2O (2.0 g.) (0.5 g.) (0.49 g.)

EXAMPLE VII Under the anhydrous conditions of Example I, 68.1 g. sodium ethoxide and 146 g. triethyl borate in 250 ml. of ethanol gave 197 g. (92%)y sodium tetraethoxyborate, melting at 291-293" C. (d). The melting point was raised to 348-351 C. by thorough drying.

following reactions appeared to have taken place: [CH3N( 02H, 0H) 31+r+NeB (o CH3) i-e NelonariemonB-o @H311- was added all at once, withvigorous agitation, to solutionv of..4l.`5 g. tetrakis(hydroxymetliyl)phosphoniuin The: precipitate, after being Aiiltered and dried in vacuo, weighed 51 g. It contained, along with the solid obtained on evaporation of the filtrate, 69% of the tl'seoretical yield of condensed phosphonium tetraalkoxyborate polymer, intrinsically similar to the major product of Example VL As in Example VI, the remaining portion of the phosphonium salt had been decomposed to alcohol-soluble products.

EXAMPLE IX Twenty grams of sodium tetramethoxyborate in 200 ml. absolute ethanol was refluxed 45 minutes and then distilled through a l-plate column at atmospheric pressure until 100 ml. of distillate had been collected. The still pot residue was evaporated dry in vacuo to yield 25.7 g. (95%) sodium tetraethoxyborate, melting at S35-341 C. Withrdecomposition, identical with the product of Example VII.

NaB 4+ 4 EXAMPLE X Ethylene bromohydrin, `25 g., and triethanolamine, 29.8 g., were mixed to give a clear solution. After heating this solution on a steam bath for 5 hours, a crystalline slurry was formed. This was triturated cold with 25 ml. methanol, land filtered free of 4.7 g. triethanolamine hydrobromide, melting at 178-184 C. The combined iiltrate and wash was diluted with 28 ml. chloroform, cooled, and ltered to yield 37.3 g. (68%) tetrakis(2- hydroxyethyl)ammonium bromide, which appeared as colorless deliquescent crystals melting at 92-96 C. (Br: Found, 28.4%; Calc. 29.1%).

A 9.47 g. quantity of the product of Example I in 25 m1. methanol and 16.5 g. of the product of Example X in 25 ml. methanol were mixed at 20 C. to give a clear solution. Evaporation of this solution to dryness quickly, `first at approximately C. and then at room temperature to constant weight, gave 21.8 g. glassy foam, melting with decomposition at Z55-275 C. The foam was deliquescent, Water soluble (alkaline reaction) and soluble in cold methanol. Since the sodium bromide formed cannot be found by X-ray methods, the product is, as determined by stoichiometry, largely the sodium bromide adduct of 6,6-bis-(2-hydroxyethyl)-2,2dimethoxy1,3dioxa- 2-bora-6-aza-cyclooctane betaine Treatment with a stoichiometric amount of silver nitrate precipitated the requisite amount of silver bromide; as shown below:

.tgBr-tNaNotHnocmin-(ointonsone The salt-free organic product decomposed with melting at approximately the same temperature as the adduct.

Since the initial product started to lose volatile liquids at 130 C., it was held in vacuo at 170 C. for approximately 11/2 hours, by which time it had lost 99% of the theoretically available methanol:

The almost colorless, glassy, polymeric residue sintered at 185 C. and melted with decomposition at Z50-260 C. Its properties were similar to those of the first product except that it was insoluble. in methanol and gelled very slowly in ethanol. Although the devolatilized product was readily water-soluble, it was not readily hydrolized. From an aqueous solution held at C. for three hours there was recovered the initial weight of product, having an unchanged decomposition point (Z50-260 C.) but a somewhat greater rate of methanol solubility than did an untreated sample of polymer.

EXALLPLE XII Sodium tetramethoxyborate, 27.1 g. in 50 ml. methanol, was added to tetraethylammonium bromide, 36.1 g. in 50 ml. methanol. There was no apparent reaction. Evaporation in vacuo gave a total of 60.3 g. solid recovered; 95.5% of the starting weight. An aliquot of this, extracted with hot chloroform, left as residue a nearly quantitative yield of sodium tetramethoxyborate. Chilling the chloroform extract produced an equivalent weight of almost pure tetraethylammonium bromide, melting at approximately 270 C. and containing 37.6% bromide (pure product melts at 276 C. and contains 38.04% bromide). There has, therefore, been no reaction.

EXAMPLE XIII By the procedure of Example IV, 18.3 g. tetrakis-(Z- hydroxyethyl)ammonium bromide and 14.3 g. silver chloride gave tetrakis-(Z-hydroxyethyl)ammonium chloride, 14.2 g. of colorless deliquescent crystals, representing a 93% yield of 98% pure product.

which may be called 1-(2-hydroxyethyl)-5-etl1oxy-1-aza- 5 bora 4,6,11 trioxabicyclo-[3.3'.3.] undecane betaine. Fractionation from acetone-alcohol mixtures served to purify these products. The product mixture melted with decomposition lat 2SC-236 C. (in a sealed capillary tube). However, on being heated to 148 C., and again at 197201 C., it lost more alcohol. This can be attributed to polymer formation:

-CaBsOH These polymers may well be mixtures of cyclic and acychc chains.

15 Y EXAMPLE XV l A group of commercially available products sold under the tradeV name Ethoquad are reported by' their manufacturer to have the general formula ('JHa RN-(ognionn o1- (C2H40)yH where R is a saturated or unsaturated normal alkyl chain of 8-24 carbon `atoms (or a mixture of such chains), and x rand y are integers such that their sum can vary from two to fifty or more. These products are made by reacting primary fatty amines with controlled amounts of ethylene oxide, then quaternizingV the resultant oniom with methyl chloride. The products are therefore complex mixtures in which the number of carbon atoms in R,

and the values of x and y and x plus y all vary. Thus Ethoquad 18/12 is reported by its manufacturer to be (CgHrOhH where'x plus y=2. Including its shipping solvent, the product is reported to have'an approximate molecular weight of 422, an amine-l-amine hydrochloride content of no more than 2%, and a quarternary content of 74- 76%. Since the octadecyl residue came initially from the stearoyl or oleyl groups in fats, or the mixed C15-C18 acid residues in tall oil, it contains limited quantities of ClHSf, C18H35* `and possibly C20I141 groups. In addition, the value of x plus y, given as 2, represents only an average value. Since the addition of ethylene oxide to an amine results in a (roughly) Gaussian distribution, the product Will contain individual compounds in which x and y vary from zero to possibly five. In this case, however, where onlyy a Very limited quantity of ethylene oxide is used (two moles per moleof amine) it is safe toassume that VEthoquad 18/12 is indeed principally Commercial Ethoquad 1%2, 272 g. was purified by slurrying in 200 m1. acetone in a Waring Blendor, filtering, washing with 100 m1. (CH3)2CO, and vacuum drying. The resulting material, 130 g., was primarily octadecylmethyl-bis (2 hydroxyethyl)ammonium chloride, 96-97% pure by chloride determination, in the form of a free-ii'oWing'o-White powder, completely melting at 85 C.

A 93 g. quantity ofV purified Ethoquad 1%2 in 100 ml. methanol was mixed with 34.5 g. of the product of Example I in 70 ml. methanol (immediate white precipitate). The reaction mixture was poured into 300 ml. benzene and then ltered to remove 11.0 g. sodium chloride (86.7% of theory). Evaporation in vacuo at approximately 70-80 C. gave 100.1 g. formed product; an off-f White powder, very largely C Hg C 2H.; O O C Hs C isHsvN Unlike the `starting 'Ethoquad, it was soluble in ether, benzene, xylene, and tetrahydrofuran, and insoluble in hot acetone and. hot dimethylformamide. A methanol (100ml.) solution of 45.3 g. product was treated with 7.08 glacial acetic acid to lower the solution pH from 9.43 to 7.0, then evaporated dry in vacuo at 25 C., `slurrie'd in acetone and reevaporated to dryness. A more stable product, weight 45.9 g., was formed, which developed less odor and lost less weight in storage in vacuo than did an untreated sample. This can be attributed to the conversion `of the methoxide salt impurity to a more stable salt:

CisHs-l O CH3 CisHsy OHOH-l-(Ho ofnorNJbzHioBb'oimNicrrnon).

(CHaoonoon,

EXAMPLE XVI lWhen the preceding example was repeated using ethanol as the reaction medium to precipitate out Isodium chloride moreV completely, partial transesterication with the solvent occurred.

A 7.25 g. quantity of sodium tetramethoxyborate in 50 ml. absolute ethanolV was mixed with 18.7 g. of 97% pure Ethoquad 1%2 in 50 m1. alcohol to give an immediate precipitate of '2.23 g. (86% of theory) of sodium chloride. -No further precipitation occurred on holding the ltrate' at 40 C. It can be seen that use of a solvent in which NaCl was less soluble did not result in more cornplete precipitation` of NaCl. The liltrate was evaporated to constant Weight atroom temperature in vacuo, giving 25.5k g. of a glassy residue. Since this is -approximately 7% greater than the theoretical, and a careful examinationV failed to disclose the presence of any free solvent or methanol, the solvent must have entered into the reaction, e'.g.:

Assuming that no transesterication of onium hydroxyl groups with borate alkoxy groups had occurred during evaporation, the ganin Weight would represent an average value of x as being somewhat less than one. Sincean undetermined amount of condensation had undoubtedly occurred, the true value of x as 4an average is unknown.

The glassy residue, redissolved in 100 ml. of chloroform, gave no precipitate of sodium chloride on dilution with an equal volume of hexane. From X-ray draction studies slightly more than 6 milli-moles of sodium and chlorine, .approximately one-eighth of the starting amounts, is tied up in'adducts, e.g.

ornomorr o om oiiHNorucrnoBlo ogm Evaporation of the solution to dryness gave 21.8 g. of

- olf-white foam, which was pulverized to a non-hygroscopic wax that sintered Vat 102' C. and ran clear at 122 C. By stoichiometry, it was established that the major component probably was the 2,2dimethoxy6 methyl-6 octadecyl-1,3 diox-a-2-bora 6-aza-cyclooctane betaine obtained in the preceding example. It was soluble in water, ethanol, chloroform, tetrahydrofuran and benzene, but insoluble in dimethylformamide, ethyl acetate, acetone, and dioxane. lts aqueous solution was alkaline in reaction; acidiiication with eg. dilute nitric acid greatly increased its viscosity.

EXAMPLE XVIII Sodium tetramethoxyborate, 73.5 g. in 150 ml. hot methanol, and purified Ethoquad 18/12, 200 g. in 150 ml. hot methanol, was mixed, held at reilux a few minutes, and then allowed to cool down overnight to give, on filtration, 19.1 g. sodium chloride. The ltrate, on

diluting with 1000 ml. benzene and chilling to C.,V

gave an additional 3.8 g. NaCl (total, 22.9 g.=84% of theory). The ltrate was evaporated to dryness; rst at atmospheric pressure, then at room temperature to a 20% reduction in volume, and finally at Sil-60 C. in vacuo to a constant weight of 218.7 g. This is only very slightly less than the theoretical weight (220.8 g.) obtainable if two moles of methanol were evolved per mole of reactant, e.g.

In addition, the analytical data support the above structure (calculated: B, 2.44%; N, 3.2%; Found: B, 2.9%; N, 3.1%). Nevertheless, the dried product was a mixture; recrystallization from acetone gave an appreciable quantity of tan solid that melted with discoloration at about 160 C. and had the correct boron and nitrogen analyses for the structure:

Calculated: B, 3.6%; N, 2.33%. N, 2.3%.

The infrared spectra of both recrystallized and unrecrystallized products showed absorption maxima in the 9.2 and 10.3 micron region, which was believed to be characteristic of the EXAMPLE XVIII A fatty quaternary ammonium chloride available commercially as Ethoquad 0/25 is claimed by its manufacturer to be a methyloctadecenylpolyethoxy product of the formula im i [CrtHssN-(CLO l xHlCl" where x plus y averages 15. Ey this is meant that, for every mole of octadecenylamine, an average of 15 moles of ethylene oxide was consumed in the preparation of the Ethoquad This means that even 'analytically pure Ethoquad 0/25 is a complex mixture in which x and y can each vary from zero to at least thirty, and therefore the sum x plus y can vary from zero to, say, sixty.

18 However, the statistically averaged product is, according to its manufacture, a 95% pure octadecenyl quaternary salt in which x plus y=15, representable for no reason other than convenience as A solution of 15.8 g. sodium tetramethoxyborate in 50 ml. of methanol was added to 100 g. of solvent-free Ethoquad 0/25 and mixed. The resultant slurry of tine solid in thick liquid was diluted with 100 ml. of dry benzene, and allowed to sit overnight. Sodium chloride (2.81 g.=48% of the theoretical yield) was ltered o, and the filtrate was evaporated (on a steam bath) in vacuo to constant Weight.Y HThe evaporation residue,V 104.4 g. of clear, tan, rigid gel, could not be converted to a solid by further drying in vacuo at room temperature (even over P205) or by chilling. Its nal weight checks quite well with that expected on the loss of two moles of methanol per mole of each reactant. On the basis of stoichiometry and analytical data, the product is probably a mixture of almost equal weights of Htc (ormoni-(00H93 EXAMPLE XIX A product available commercially as Ethomeen C/ 12" is described by its manufacturer as being cocobis(2 hydroxyethyD-amine; RN(C2H4OH)2, where R, being derived from coconut fatty acids, consists of the homologous normal alkyl group C8H1T, C1OH21-, C12H25- (major component), C14H29, C16H33, and C18H37 with a small amount of C18H35.

A mixture of 152 g. Ethomeen C/ 12 and 76 g. pure benzyl chloride was held at 90 C. for ve hours and then allowed to stand overnight. It was stripped at -100 C. and 2-3 mm. of Hg vacuum for four hours to give 213.5 g. (99% of theoretical) of benzyl-cocobis-(2-hydroxyethyl)ammonium chloride.

as a clear, viscous orange oil which slowly solidified on standing. Recrystallization from ethyl acetate gave colorless platelets, running clear at about 99 C.

EXAMPLE XX A solution of 6.4 g. sodium trimethoxyhydroborate, NaBH(OCH3)3, in 50 ml. methanol was mixed with a solution of 21.5 g. of the product from Example XIX in 50 ml. methanol. A white precipitate was immediately formed, which was removed by ltration. Evaporation of the iiltrate to constant weight gave a product which unexpectedly had none of the active hydrogen expected in, e.g.

R\ /CHaCHzO H B-oom Thus, the reaction of sodium trimethoxyhydroborate with agresor i' 19 methanol had been completed before its metathesis with theV quaternary':

below 360 C. and was readily solub-le lin water (with hydrolysis) and methanol, but insoluble in boilingethanol, ethyl acetate, diglyme and dimethylformamide. Its identity was established by X-ray diifraction, which also showed CH2 C 51H5 HgCsHs EXAMPLE XXI Following the general procedure of Example l, sodium metal, 11.5 g. was dissolved in refluxing pure isopropyl valcohol under an atmosphere of dry N2, and then treated dropwise overr45 minutes at reilux (with stirring) with 103.4 g. `freshly distilled isopropyl borate. VRelluxing and stirring were continued for an additional 90 minutes; 'the mixture was then cooled and filtered. The white crystals of sodium tetraisopropoxyborate, washed under anhydrous conditions with isopropyl alcohol and. a vacuum dried, weighed 118 g. (87.5% of theory) and melted at 287-292 C. with decomposition. The product was insoluble in tetrahydrofuran and 2-propanol, slightly soluble in diglyme, and very soluble in mixtures of diglyme with the other two solvents. On being exposed to air, it was rapidly hydrolized.

To a stirred slurry of 27.0 g. sodium tetraisopropoxyborate in 400 inl. isopropyl alcohol was added in a thin 4stream a solution of 43 g. `of the cocobenzyl vsalt of Example XX dissolved'in 100 2-prop-anol. Stirring was continued in `a sealed vflask for 2 hours; then the mixture was allowed to stand overnight. Filtration gave 5.3 g. sodium chloride, 91% of the theoretical yield. Vacuum evaporation of the ltrate to constant weight at room temperature gave 45 .6 g. of product as light brown foam. It was very hygroscopic, and soluble in water and chloroform. The stoichiometry and the analytical results indicate that the product was largely HBCUCHs 02H40 OCH(CHa)a However, the `data do not exclude -at least two other possibilities, the macrocyclic polymer O 02H7 CHzCes- In and its borate-terminated derivative OC3H1 CHzCeHg; Ix

EXAMPLE XXIII 02H40 O CBB the presence of atminor quantity of sodium aluminate, NaAlO'Z.

EXAMPLE XXIV A 25 g. quantity of the product of Example XXIII and 43 g. of the product of Example MX, each in 100 ml. isopropyl alcohol, were mixed and stirred in a sealed ask overnight, and then ltered to give 4.7 g. (81.2%) sodium chloride, contaminated with about 23% of its weight of alumina or sodium alurninates.V Evaporation of the iiltrate to constant weight at room temperature and 2-3 mm. of Hg pressure gave a light yellow, viscous liquid, largely HsCaCHn OCaHy +NC2HaO-AP`O CaH7 Y -coco nHiOH 0C3H7 by stoichiometry.

Continued reaction at 2-3 mm. and.90-100 C. gave eventually 43.3 g. of a clear` amber, hygroscopic gel, soluble in benzene, acetone and dry alcohols. The stoichiometry and chemistry indicate that the major component of the product is the more or less completely condensed polymer. However, structure determination was made almost impossible due to the great susceptibility of the product to hydrolysis to form [S3-alumina, AIZOHHZO.

EXAMPLE XXV The textile softener commercially available as Catanac SP was purified to give dry dimethyl-)EZ-hydroxyethyl-S- (stearoylamino)propylammonium dihydrogen phosphate,

CH3 Y (CUHssC ONHCslNCgHlOH) H21 O4 51.1 g. of this material in 50 ml. methanol were mixed with 15.8 g. sodium tetramethoxyborate in 50 ml. methanol to give an immediate gelatinous precipitate. It was stirred well, then allowed to stand overnight. Filtration gave 8.1 g. (67.5% of the theoretical) sodium dihydrolgen phosphate. Vacuum evaporation of the filtrate at room temperature to constant weight gave a soft paste, the major component of which was the unesteriiied salt, dimethyl ,8 hydroxyethyl-3-(stearoylamino)propylammonium tetramethoxyborate. Further heating in vacuo at -100" C. gave a light yellow Wax which had the correct nitrogen content for the monoester:

ons oon: owHaooNnoaHNoiHlo;ooH

om oom (Calculated: N, 5.42%; Found: N, 5.6%.) It undoubtedly contained compensating quantities of other products.

EXAMPLE XXVI Twenty-three grams of tetrakis-(Z-hydroxyethyl)ammonium chloride in m1. of isopropyl alcoholand twenty-tive` grams Vof sodium tetraisopropoxyaluminate in an equal amount of the same solvent were stirred in 'a sealed ilask for 42.5 hours and then filtered. The vacuum-dried residue, weight 29.9 g., was shown by analysis to contain the theoretical yield (5.85 g.) of sodium chloride, a trace of unreacted tetra-isopropoxyaluminate, and a near theoretical yield of the condensates obtained by an average loss of three moles of alcohol. The organic condensate, on the basis of chemical and analytical reactions, appeared to consist very largely of the one compound 1 (2-hydroxyethyl)-5-isopropoxy-1-aza5a1umina4,6, 11-trioxabicyclo[3.3.3lundecane betaine.

which was separated from the sodium chloride by extraction with isopropyl alcohol. This hygroscopic product melted at 220-225 C. with charring. It was very soluble in water and soluble in methanol, but only 0.2% soluble in cold 2propano1.

EXAMPLE XXVII A magnetically stirred ask, equipped with a gas exit tube leading to a gas collector was charged, under anhydrous conditions, with 100 m1. of dry bis-(Z-methoxyethyl) ether, 11.5 g. tetrakis-(2hydroxyethyl)-ammoni um chloride, and 6.5 g. sodium trimethoxyhydroborate. The mixture was stirred for 24 hours, during which time 34.6% (388 ml.) of the theoretical amount of hydrogen to be obtained from the reaction was caught in the gas collector. Filtration and vacuum drying gave 18.3 g., a quantitative yield, of a solvated mixture of sodium chloride, 2[tris-(2hydroxyethyl)am monio]ethoxytrimethoxyborate betaine, and 2[tris-(2- hydroxyethyl) ammonio]ethoxydimethoxyhydroborate betaine in approximately a 1:2:3 weight ratio. The overall reaction is therefore and EXAMPLE XXX A solution of tris-(2-hydroxypropyl)amine, 121.3 g. in 100 ml. of methanol, was treated with 100 g. of methyl iodide, and allowed to stand overnight. It was then reuxed for six hours, and allowed to cool overnight. Vacuum evaporation at SiO-100 C. gave 203.4 g. of clear amber oil which, after being extracted three times 'with ether and vacuum dried, gave 172.8 g. (82% of the theoretical yield) of methyltris-(2-hydroxypropyl)ammonium iodide, 97% pure by iodine determination.

EXAMPLE XXXI Following the procedure of Example IV, 100 g. of

EXAMPLE XXVIII To demonstrate the hydrolytic stability of the novel products of Example XXVII, 5.0 g. of the mixed condensates was dissolved in 10 ml. of water in a ask to which was connected a gas collector. Very little gas was evolved from this solution at room temperature. Sodium trimethoxyhydroborate, in a similar alkaline solution at room temperature, showed only slightly greater gas evolution. On acidification of the rst solution with ten drops of concentrated hydrochloric acid, and allowing the solution to stand at room temperature, there was evolved a total of 15 ml. of hydrogen, 6.1% of the theoretical amount based on the B-H content of our novel product. Under similar circumstances, at least 30% of the sodium trimethoxyhydroborate was converted to methyl alcohol, sodium chloride and diborane (which igm'tes in water). The acidied rst solution, on being held at 60 C. ifor six hours, evolved only 160 ml. of hydrogen (total), 65% of the theoretical. Sodium trimethoxyhydroborate in acid solution was completely destroyed within iifteen minutes at 60 C.

EXAMPLE XXIX To demonstrate the thermal stability of our products, even when they contain B-H bonds, 5 .O g. of the product of Example XXVII heated at carefully controlled temperatures in a small distillation Flask. On being carefully heated, virtually no gas was evolved until the product reached its sintering point, 85 C. At that temperamethyltris-(Z-hydroxypropyl)ammonium iodide and 51.6 g. of freshly prepared silver chloride gave a quantitative yield of pure methyltris(2-hydroxypropyl)ammonium chloride:

EXAMPLE XXXII A solution of 24.2 g. methyltris-(2-hydroxypropyl)arnrnonium chloride in ml. of 2propanol was added under anhydrous conditions to a slurry of 27.0 g. of sodium tetra-isopropoxyborate in 100 ml. of the same solvent, and the mixture was stirred in a sealed ask overnight. Filtration through sintered glass, under a rubber dam, gave as residue a quantitative yield (5.8 g.) of sodium chloride. The filtrate, on vacuum evaporation at room temperature, gave 26.7 g. of hygroscopic brittle foam, a mixture of products which had lost on an average of three moles of 2-propanol per mole of product. That it is a mixture of products is clearly shown by the following fractionation experiment:

The product, as a clear, amber solution in 50 ml. of 2pr0panol, was diluted with 270 m1. of acetone to precipitate Fraction 32-1. The filtrate from this fraction was treated with 100 ml. more acetone to precipitate Fraction 32-2. Treatment of successive ltrates with 100 ml. portions of acetone gave as solid precipitates '23 24 Fractions 32-3A and 32-4. The ltrate from Fraction moles of methanol in each mole of condensate. That the 32-4 required 200 ml. of acetone to precipitate an appreproduct was largely the monocyclic betaine ciable quantityof solid (Fraction 325).' Evaporation f of the filtrate from Fraction 32-5 in high vacuum at CH3 j 90--100 C. gave Fraction 32-6. `A summary of the '6 f Y y @Hiv/CH2 HO\ /OCH fractionation results is 'giveninTable C. j' /B\ TABLE C HoCHe a/ etileno H Y CH2 CH3 Fraction Number 'Weightin Melting '10 Arather than less lstable linear' condensates was shown Grams Rangeoo Iby theffollowingexperiment:

1A 28.0 g. quantityr of product, rcontaining 1.7 g. sodium iss-o g?" 'm :figg 13H42 chloride, was dissolved in 200 m1. reiluxing methanol and j (1)- gg then very slovvly distilled at -a reflux ratio which permitted s Y "Y ofs 12s-132 15 collection of 100 ml. of distillate in lOl/2 hours. Only a i 713-90 70-75 trace of Itrimethylborate distilled over as its azeotrope with Tonarm; 22.30 methanol; the rest of the distillate was methanol. Evaporation of the remaining liquid .inV the pot at 90-100 C. in vacuo gave further condensationto yieldv 24.1 g. of bnit- The first fraction appears to be rich in theKhigh-melting, tlc, colorless, foam. This Was'converted `to a high polyinsoluble, 1,3,7,10-tetramethyl-5-isopropoxy-1-aza-5boramer in Example XLI. Y 4,6,1l'triOXabiCyClO-[3.3.3] Ulldeane betaine, l EXAJVLPLE XXXIV CH3 l VVA. solution of' 87.7 g. 1,2-bis-(Z-hydroxypropylyanrino .ethane in 200 ml. of methanol was treated with' 93.7 g. of

l ,f CHCHO CH3 vrmethyl iodide, Yand `allowed to stand overnight. An addi- HiC-NGH2CHoB 0 CH-CHs .tional 50 ml. of methanol was added, and the mixture was` H reuxed lfor four la'ours under -a Dry Ice-cooled condenser.

Devolatill-zation gave a light yellow, viscous syrup wh1ch CHBCHO ,30 after thorough extraction with acetone `and vacuum dry-l Hs ing, gave as a pale orange viscous syrup, 138.1 g. (80% of the `theoretical yield) of 1,2-ethy1ene-bis[methyl-bis-(Z- hydroxyprojpyl) ammonium iodide] containing about 10% of the monomethiodide.

` Y EXAMLE XXXV The ethylene diquaternary salt of Example XXXIV,

The nexttwo fractions contain appreciable quantities of the Yless highly condensed*2,2-diisopropoxy-6-(2-hydroxypropyl) 4,6,8 trimethyl 1,3 dioxa 2 bora 6 -aza- 35 cyclooctane,

CH; CH3 31.2, g. in 5'0 m1. of methanol, was treated with a solution H3C CmHO OHCH, ofA 17.1 g. sodium tetramethoxyborate in 50 ml. of methay Yno1, and allowed to stand overnight. The clarified solu- /B\ 40 tion was evaporated dry to give a quantitative yield of HO CHC s CHZCHO OCHCHS brittle White foam, melting largely at 76 C., very largely H, H, CH, the uncondensed salt te im e omo /OCHs HOCHCH, CHQCVHOH CHSO\ /ooHa \B Y HaC-N-ACHz-QHQ-N--CHB /B\ onto/ \oon, H ooHo" l Y, emotion lomo oom CH3 Y om VThe successive fractions become richer apparently in and an equivalent amount of sodium iodide. Neverthehgher condensates, e,g less the sodium iodide Vsimultaneously formed could not Y be identied `as such by X-ray diffraction studies, nor

CH3 CH3 CH3 l l could 1t be separated from the organlc salt by extraction CHZCHO (|3H3 CHCHO /OCHCHS or reorystallization. The product is converted to a poly- HrCN-ornoHo-B-OCHCHQN /B\ y Ymer in Example Y Y Ha CH3 CHaCHO OCHCH 60 EXAMPLE XXXVI CHHO Ha H The dimethiodidevof Rampe Xxxrv, 121.2 g., was H converted by essentially the procedure of Example lIV to Experiment establishes that Fraction 32-6 is very largely the dimethochloride. polymeric. Y

EXAMPLE XXXVII The ethylene vdimethochloride of Example XXXVI p EXAMPLE XXXIII Following the earlier procedures, 43.3 g. of methyl-tris- (2-hydroxypropyl) ammonium chloride in 100 ml. metha- (containing about half its weight of monomethochloride), nol and 28.3 g. sodium tetramethoxyborate in the same 19.3 g. in 50 ml. methanol, was treated with 12.9 g. sosolvent gave, after dilution of ythe filtrate with 200A m1. 7.0 dium tetramethoxyborate as in Example XXXV. Reiiltraof benzene and reltration, 7.3 g. (approximately of tion after dilution with benzene gave a total of 2.4 g. the theoretical yield) of sodium chloride. The residue (50%) sodium chloride. Evaporation of the filtrate gave from vacuum evaporation of the second ltrate was 53.3 as a brittle foam 25.9 g. 'of a mixture of products averagg. of hygrosoopic, brittle, off-white foam. VThe stoichiing 2-3 moles of methanol lost in condensation.' The O'rnetry vof the reaction showed an average loss of tvvo 75 product mixture sintered at 65 C., and melted at l7 5 178 C. The polymerization of this mixture-is described in Example XXXIX.

EXAMPLE XXXVIII -corresponded to a loss of more than 6 moles of methanol.

EXAMPLE XXXIX A 10-20 g. quantity of the mixed products from Example XXXVII was dried to constant weight at room temperature and 3 mm. of mercury, giving 9.96 g. of dry condensate. This loss of weight represented very largely the water picked up by the product in handling. At 3 mm., the product was heated to 100 C. in one hour, and held there one hour; volatile products being stripped oiI" under vacuum as formed. Approximately 10% of the V'weight of the product, 0.93 g., was so lost. The product was then heated up to its liquifaction temperature, 220- 230 C., and held there for one hour; during this period 2.95 g. of product was lost in volatilization. A very small amount of high-boiling liquid had condensed on the upper part of the reactor; this portion being readily soluble in acetone and free of borate. The major part of the heat-treated solid was a tan residue, weight 6.08 g. The solid was a largely polymeric condensate presumably containing units, as Well as cross-links, since it was dispersible, rather than soluble in Water. Trituration with acetone removed .much of the color, leaving a light tan polymeric solid melting with decomposition at about 210 C.

EXAMPLE XL A procedure similar to that of Example XXXIX was followed using 7.86 g. fraction 32-6 from Example XXXII. Because of its earlier heat treatment, this condensate mixture was less hygroscopic and less capable of further condensation than the starting material used in ,Example XXXIX. At room temperature it lost only 0.01 g. At 100 C. it lost about 10% of its weight (i.e.

tone, which suggests that the major part of the mixture -was polymer containing the unit (l/Hr EXAMPLE XLI A quantity of the product of Example XXXIII initially CHzCHO/ -`'melting at 73-87 C., was dried down in vacuo at room temperature to 9.58 g. After a 100 C. heat treatment, the product weighed 8.63 g. (a 9.7% weight loss) and melted at 17080 C. After being held at 200 C., the sample had lost a total of 3.53 g. in weight (36.8%)

26 and consisted of a stringy, light tan gum, containing susfpended sodium chloride. It was only partially water soluble, but quite soluble in alcohol, less so in acetone. The properties suggest that the initial condensate was converted to a not very highly cross-linked polymer.

EXAMPLE XLII To a magnetically stirred ask equipped with thermometer and a reliux condenser was charged 100 ml. of dry, peroxide-free tetrahydrofuran, then 2.24 g. of sodium tetrahydroborate. The stirred suspension was chilled to and held at approximately C. while small portions of tetrakis(hydroxymethyl)phosphoniumchloride (totalling 11.2 g.) were washed down the condenser into the ask with a total of 50 ml. more of solvent. The slurry (protected from moisture) was stirred l/2 hour more at approximately/#70 C. and then stirred whileY it wasV allowed to come to room temperature (3 hours). It was finally warmed to 65 C. At slightly below room temperature the desired metathesis became apparent:

The crude reaction product was a very hygroscopic mixture of salts which was more reactive than either of the starting components. It was partially to completely soluble in water, alcohols, acetone, and dimethylformamide, in each case with marked gas evolution. Unlike the starting sodium tetrahydroborate, it was insoluble in the dimethyl ethers of diethylene and triethylene glycols.

The dry tetrakis-(hydroxymethyl)phosphonium tetrahydroborate, on being gently warmed as a thin layer on the bottom of a beaker, evolved highly inammable gases (principally hydrogen) at about C. to 220 C. It changed first into a liquid `and tinally into a solid. 'Ihe final polymer was a mixture of products, similar to that of Example VI but containing small amounts of active hydrogen.

EXAMPLE XLIII Two sets of five No. 4 finishing nails were degreased in n-butyl ether, dried, weighed and placed in small suction liltration flasks. In one case, the ve nails weighed 4.0581 g.; in the other the weight was 4.0485 g. A solution was prepared by dissolving in 53 ml. deionized water 0.53 g. of the polymeric mixture obtained on holding the product of Example XIV at elevated temperatures. This solution (pH 10.55) was added to the nails in Flask 43A. A control solution of sodium carbonate in deionized water, 53 ml. at pH 10.5, was added to the nails in Flask 43B. Air at room temperature was bubbled through both solutions at the same rate for 24 hours. At the end of 30 minutes, the nails in the control Flask 43B had begun to rust. At the end of 24 hours, the control liask, 43B, was opaque with rust, while its nails were pitted and rusty. Flask 43A was no more turbid than when lirst charged; the solution therein was free of rust, and the nails were as clean and free of pitting as they were 24 hours earlier. The control nails, when carefully Washed and dried, had lost 0.0162 g., or 3.99% of their initial weight. The nails protected by our novel polymer had lost only 0.0009 g., or 0.02% (within experimental error of no loss).

EXAMPLE XLTV To demonstrate the eiectiveness of our novel surfactant betaines in emulsion polymerization action, the following experiment was conducted: An emulsion of 65 parts of styrene, 35 parts alpha-methylstyrene, and commercial methyl ethyl ketone peroxide (0.8 part) was made in 180 ml. of water using 1.5 parts by Weight of the product of Example XVII. The stable emulsion was polymerized for 8 hours at 115 C., steamstripped of volatiles at C., and then coagulated by the accepted salt-acid procedure. There was thus obtained a 75.1% yield of latex, singularly free of coagulum, having a heat `distortion temperature of 196 F. There are relatively few polymerization emulsificants commercially available which produce copolymers of these two monomers in such high yields, without coagulum formation. l Y

EXAMPLE XLV In a preliminary screening test for contact insecticides, different amounts of the product of Example XXII were ground to a uniform powder with 25 parts of diatomaoeous earth (Micro-Cel 800), 2 parts dispersant (Naccanol SW) and 73 parts pyrophyllite (Pyrax). The wettable powders so obtained weresuspended in the desired amount of Water, and cranberry bean plants were dipped into the dilerent suspensions and allowed to dry. Third instar larvae of the MexicanV Bean Beetle were then caged on the treated plants and maintained under greenhouse conditions for 48 hours. After that time, observations were made of mortality, plant injury, and percent feeding. On the basis of three replicates, each vusing fifteen organisms at concentration levels of 10, 100 and 1000 p.p.m. of toxicfcondensate, it was established that the LD50 for the product of Example XXII was 80 p.p.m. No plant injury resulted, even at the 1000 p.p.m. level. Thus, the products of the invention are effective insecticides. Y

We have thus provided a new type of ionic condensate which, because of the linking of balanced, oppositely charged atoms in the molecule, is virtually incapableV of dissociation. Since the novel reaction by which these condensates are made can be conducted under conditions to provide both interand intramolecular condensation, it is possible to obtain unimers and polymers as products.

All of the products of the invention have remarkable `antistatic properties. Since they are, for the most part,

lThus the products of Examples XV, XVIII and especially XXV are not only surfactants and Vtherefore softeners, they are also textile antistatics. Polymers such as might be derived from Example XIV can be applied to metals or glass as antistatic agents.

The -unimeric products of the invention can beused as intermediates in producing the useful charged polymers if they contain substituents which are capable of further condensation. Furthermore, they are in themselves useful for a variety of practical applications. The compounds of the invention wherein the R group attached to the Q atom is a fatty, aliphatic chain of suflicient length (e.g. at least 8 carbon atoms) to counterbalance the hydrophilic nature of the betaine moiety are novel germicides, fungicides and surface active agents. These compounds are also excellent emulsicants in theemulsion polymerization of styrene. All of the unimeric products of the invention are effective acid and `alkali scavengers. They are useful, therefore, in chemical reactions where a buffering agent is required. g

The novel polymers and polymeric mixtures of the invention (or mixtures of polymers and unimers) are useful as protective coatings for pipe, metal fittings, andthe like, as is shown in Example XLIII. The mixtures of the materials, the composition of which Vcan be controlled either by varying the reaction `conditions or by blending the products of the invention, Vare especially useful, since they provide for lexibility in the particular physical properties of the ultimate product. Since the polymers of the invention are water-soluble, they are easily applied .to a

given metal substrate from aqueous solution by sprayform the heterocycle wherein Y is a cation selected from the group consisting of the metals of groups 1A and 2A of the periodic table; R is a member selected from the group consisting of hydrogen, lower alkoxy, -(CH2'nO)mQ+R3 and V[-(CH2nO)mQR3] +X, wherein X is an anion of a strong acid; and R and R' when taken collectivelyy with the Q and M on which they are respective substituents form a heterocycle of the group consisting of and 2. Compounds according to claim 1 wherein Q is N,

VM is B, two vof the R substituents are acyclic hydrocarbon radicals having up to 20 carbon atoms, two of the R' substituents are lower alkoxy, and the remaining R substituent and R substituent complete the heterocycle 1nd MR", I f

' ionnnof.' Y 3. Compounds according to claim 1 wherein Q is N, M is B, twoy of the R substituents are '(CnHgnOLnH, two of the R substituents are (CH2nO)mQR3, and the remainingY R substituent and R' substituent complete the heterocycle 4. Compounds according to claim 1 wherein Q is N, M is Al, one R substituent is hydroxy lower alkyl, vone R substituent is benzyl, the remaining R substituent is an acyclic hydrocarbon radical having up to 20 carbon atoms, and the three R' substituents are lower alkoxy.

5. Compounds according to claim 1wherein Q is N, M is BV, the three R substituents are-(CH2O)mH, two R' substituents are lower alkoxy, and the remaining R substituent is hydrogen.

6. Compounds according to claim 1 wherein Q is P, M is B, one R substituent is-(CnH2nO)mQR3, one R is alkoxy, and the two remaining R substituents and the two remaining R substituents are taken collectively to (cannon 4 mi-tonnnmm-Mn" (Gannon 7. 2,2 dimethoxy 6-methy1-6-octadecy1-1,3-dioxa-2- bora--azacyclooctane betaine.

8. Polymerized 2,2 dimethoxy 6,6-bis-(2-hydroxyethyl)-2-bora-6-aza-1,3-dioxacyclooctane betaine.

9. 2 [benzyl"cocohydroxyethy1ammonio] ethoxy-tri-Z-propoxyaluminate betaine.

10. 2 [tris-(Z-hydroxyethyl)ammonio1ethoxydimeth oxhydroborate betaine.

11. Polymer-ized 1 hydroxymethyl-4-methoxy-1-phospha-4-bora-3,5,8-trioxabicyc1o [2.2.2.] octane betaine.

12. Method of making condensed metal ester betaines comprising reacting in an inert organic liquid medium a compound of the formula:

an anion of a strong acid; with a compound of the formula:

. Bl Y+ n n-R' wherein M is a member selected from the group consisting of tetracovalent negatively charged boron and aluminum atoms; R is a member selected from the group consisting of hydrogen and lower alkoxy; and Y is a cation selected from the group consisting of the metals of groups 1A and 2A of the periodic table.

13. Method according to claim 12 wherein the reaction is conducted at a temperature between about -180 and 250 C.

VY14. Method according to claim Y12 wherein the reaction is conducted under sub-atmospheric pressure at a temperature between about 125 and 250 C. and polymerio products are obtained.

15. Method according to claim 12 wherein the reaction is conducted at a temperature between about 0 and 60 C. and unmeric products are obtained.

No references cited.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,976,307 March 21, 1961 Bernard Rudner et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column l, lines 62 to 65, the left-hand portion of the formula should appear as shown below instead of as in the patent:

columns 5 and 6, TABLE A, structure number 7 should appear as shown below instead of as in the patent:

[n-C16H33P (CH2CHOHCH2CH3) 3] +Br column 9, lines 36 and 37, the extreme left-hand portion of the formula should appear as shown below instead of as in the patent:

CH: zuozuorcnfd-nonn same column 9, line 7 5, for weigh read -weight-; column 10, line 27, for stoichiomertic read -stoichiometrie-; line 34, the formula should appear as shown below instead of as in the patent:

[(CH3) EPCHZCHZOH] same column 10, line 39, for stoiehiomertic read -stoichiometric-g column 12, line 9, the formula Should appear as shown below instead of as in the patent:

column 13, line 46, for -2,2-dimethoXyl,3- read 2,2diInethoXy-1,3-; column 15, line 65, for formed read oamed-; Columns 21 and 22, line 45, the extreme lefthand portion of the formula should appear as shown below instead of as in the patent:

NaBH(OCH3)3 column 24, line 28, for Dry Ice-cooled read dry iee-oooled-; column 25, line 39, after the closing bracket of the formula insert a Sub X; line 47, for fraction read -Fraetion--; column 26, line 22, for that portion of the formula reading [BH4] +NaCl read [BIL] -l- NaCl column 28, line 10, for aluminium read -alu1ninum-; line 23, for that portion of the formula reading Qi-R3 read QRS-g Column 29, lines 7 and 8, for -ethoxydimeth oxhydroborate read -ethoxydimethoxyhydroborate Signed and sealed this 12th day of September 1961.

[SEAL] Attest:

ERNEST W. SWIDER,

Attestz'ng Ooer.

DAVID L. LADD,

O'Ommz'ssz'oner of Patents.

UNITED STATES PATENT OFFICE' Certificate of Correction Patent No. 2,976,307

Bernard Rudner et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 12 lines 62 to 65, the left-hand portion of the formula should appear as shown below lnstead of as in the patent:

columns 5 and 6, TABLE A, structure number 7 should appear as shown below instead of as in the patent:

[n-ClSHSaP (CH2CHOHCH2CH3) 3] +Br column 9, lines 36 and 37, the extreme left-hand portion of the formula should appear as shown below instead of as in the patent:

CH: 2[(CQH5)3PCH2(IJHOH1+ same column 9, line 75, for weigh read weight; column 10, line 27, for stoichiomertic read -stoichometric-; line 34, the formula should appear as shown below instead of as in the patent:

[(CH3) aPCHzCHZOH] same column 10, line 39, for stoichiomertic read -stoichiometric-; column 12, line 9, the formula should appear as shown below instead of as in the patent:

Ag1+ [ol-iamozmoH) 3] +01- column 18, line 46, for -2,2dimethoxyl,3- read 2,2dimethoXy-l,3-; colunm 15, line `65, for formed read -oamed-5 columns 21 and 22, line 45, theextreme lefthand portion of the formula should appear as shown below instead of as 1n the patent:

laamoom)3 column 24, line 28, for Dry Ice-cooled read -dry ice-cooled-; column 25, line 39, after the closing bracket of the formula insert a sub X; line 47, for fraction read -Fraction-; column 26, line 22, for that portion of the formula reading [BH4] -I- NaCl read [BIL] +NaC1 column 28, line 10, for aluminium read -aluminum-; line 23, for that portion of the formula reading Qd-R3 read Q,R3-; column 29, lines 7 and 8, for ethoXyd1meth oxhydroborate read ethoxydimethoxyhydroborate Signed and sealed this 12th day of September 1961.

[SEAL] Attest:

ERNEST W. SWIDER, Attestz'ng 0776061'.

DAVID L. LADD,

'omnssioner of Patents.

March 21, 1961 

1. COMPOUND OF THE FORMULA: 